EP3625182B1 - Verfahren zur herstellung gekrümmter glaslaminatartikel mit trennmaterial und produkt - Google Patents

Verfahren zur herstellung gekrümmter glaslaminatartikel mit trennmaterial und produkt Download PDF

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Publication number
EP3625182B1
EP3625182B1 EP18730509.9A EP18730509A EP3625182B1 EP 3625182 B1 EP3625182 B1 EP 3625182B1 EP 18730509 A EP18730509 A EP 18730509A EP 3625182 B1 EP3625182 B1 EP 3625182B1
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EP
European Patent Office
Prior art keywords
glass
sheet
separation
mol
glass material
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EP18730509.9A
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English (en)
French (fr)
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EP3625182A1 (de
Inventor
Douglas Dale BRESSLER
Theresa Chang
Allan Mark Fredholm
Michele Marie-Louise Fredholm
JR Louis MATTOS
Jason Scott STEWART
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Corning Inc
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Corning Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
    • C03B40/02—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it by lubrication; Use of materials as release or lubricating compositions
    • C03B40/033—Means for preventing adhesion between glass and glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C03B23/0252—Re-forming glass sheets by bending by gravity by gravity only, e.g. sagging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the disclosure relates generally to forming a curved glass laminate article, and specifically to processes for co-forming (e.g., co-sagging) glass sheets utilizing a bend-dot reducing separation material.
  • Curved glass laminate sheets or articles find use in many applications, particularly as for vehicle or automotive window glass.
  • curved glass sheets for such applications have been formed from relatively thick sheets of glass material.
  • the glass materials may be shaped to the desired shape/curvature via a co-forming process, such as a co-sagging process.
  • EP 0 414 232 A1 discloses a method of bending glass plates for a laminated glass wherein two glass plates for a laminated glass are simultaneously bent.
  • a colorless transparent glass plate 2a having a thickness of 1.8 mm was put and a glass plate 2b which is a bluish transparent heat ray absorptive glass and having a thickness of 1.8 mm was put under the glass plate 2a interposing silica powder as a lubricating powder.
  • US 3 282 772 A discloses a laminated structure consisting of two sheets of glass and a polyvinyl butyral interlayer interposed between the glass sheets and bonded thereto to provide a unitary structure, one of said glass sheets having a thickness in the range of 3.3mm inch to 4.3mm, the second glass sheet having a thickness in the range of 1mm to 2.8mm.
  • the glass sheets have a thickness difference of at least 2.5 times.
  • the invention relates to a process for forming a curved glass laminate article with the features of claim 1 and a curved glass laminate article made by the process.
  • One embodiment of the disclosure relates to a process for forming a curved glass laminate article.
  • the process includes applying a separation material onto at least one of a surface of a first sheet of glass material and a surface of a second sheet of glass material.
  • the process includes placing an outer region of the first sheet of glass material into contact with a support surface of a shaping frame.
  • the shaping frame defines an open central cavity surrounded at least in part by the support surface.
  • the process includes placing the second sheet of glass material onto the first sheet of glass material such that the separation material is located between an upper surface of the first sheet of glass material and a lower surface of the second sheet of glass material, and the first sheet of glass material and the second sheet of glass material are both supported by the shaping frame.
  • the process includes heating the first sheet of glass material, the separation material and the second sheet of glass material together while supported by the shaping frame such that central regions of the first and second sheets of glass material deform downward into the open central cavity of the shaping frame.
  • the first sheet of glass material has an average thickness, T1
  • the second sheet of glass material has an average thickness, T2.
  • T1 is at least 2.5 times T2.
  • An additional embodiment of the disclosure relates to a process for forming a curved glass laminate article.
  • the process including spraying a separation material onto at least one of a surface of a first sheet of glass material and a surface of a second sheet of glass material.
  • the process placing an outer region of the first sheet of glass material into contact with a support surface of a shaping frame, and the shaping frame defines an open central cavity surrounded at least in part by the support surface.
  • the process includes placing the second sheet of glass material onto the first sheet of glass material such that the separation material is located between an upper surface of the first sheet of glass material and a lower surface of the second sheet of glass material, and the first sheet of glass material and the second sheet of glass material are both supported by the shaping frame.
  • the process includes heating the first sheet of glass material, the separation material and the second sheet of glass material together while supported by the shaping frame such that central regions of the first and second sheets of glass material deform downward into the open central cavity of the shaping frame.
  • the first sheet of glass material is formed from a first glass composition and the second sheet of glass material is formed from a second glass composition different from the first glass composition.
  • An additional embodiment of the disclosure relates to a process for forming a curved glass laminate article.
  • the process includes depositing a separation material onto at least one of a surface of a first sheet of glass material and a surface of a second sheet of glass material.
  • the process includes placing an outer region of the first sheet of glass material into contact with a support surface of a shaping frame, the shaping frame defining an open central cavity surrounded at least in part by the support surface.
  • the process includes placing the second sheet of glass material onto the first sheet of glass material such that the separation material is located between an upper surface of the first sheet of glass material and a lower surface of the second sheet of glass material, and the first sheet of glass material and the second sheet of glass material are both supported by the shaping frame.
  • the process includes heating the first sheet of glass material, the separation material and the second sheet of glass material together while supported by the shaping frame such that central regions of the first and second sheets of glass material deform downward into the open central cavity of the shaping frame.
  • the separation material comprises a solid lubricating material that decreases friction between the first and second sheets of glass material.
  • the first sheet of glass material has an average thickness, T1, and the second sheet of glass material has an average thickness, T2. T1 is different from T2.
  • the first sheet of glass material is formed from a first glass composition and the second sheet of glass material is formed from a second glass composition different from the first glass composition, and the first glass composition has a viscosity during heating that is different from a viscosity of the second glass composition during heating.
  • An additional embodiment of the disclosure relates to a curved glass laminate article made by any of the method(s) and/or system(s) disclosed herein.
  • various embodiments of a system and method for shaping, bending or sagging a stack of glass sheets for formation of a curved, glass laminate article are shown and described.
  • conventional processes for forming curved, laminated glass articles involve heating a pair of stacked glass plates or sheets on a forming ring to near the softening temperature of the glass until the glass has sagged to the desired shape and depth.
  • a separation material is used as a separation layer between the two glass sheets preventing the glass sheets being bonded /fused together during heating.
  • co-sagging processes have a variety of advantages (e.g., improving shape matching between the glass sheets that will form the laminate, efficient use of heating equipment, process throughput, etc.), co-sagging often produces optical defects known in the industry as bending dots.
  • bending dot formation is believed to increase as the contact pressure between the two glass sheets is increased during co-sagging.
  • This increased contact pressure during co-sagging may be a function of viscosity and/or thickness differentials between the two glass sheets in the stacked arrangement.
  • Increased contact pressure is believed to stem from the different shapes that different glass sheets may form during sagging. As shown in FIG. 6 , when a sheet of glass is sagged under gravity by itself, a thicker glass sheet 100 will produce a more parabolic shape. While, as shown in FIG.
  • a thinner glass sheet 102 will produce a "bath tub" like shape where curvature is greatest near the edges and is reduced near the center.
  • contact pressure is increased near the edges when a thin ply is sagged on top of a thick ply, and contact pressure is increased near the center when a thick ply is sagged on top of a thin ply.
  • This increase in contact pressure is thought to contribute to the creation of bending dot defects through increasing imprintation of the separation material particles into the glass surfaces.
  • the difference in sag shape illustrated in FIGS. 6 and 7 generally will increase as the thickness difference and the viscosity difference between the two glass sheets increases, and thus, the sensitivity to bending dot formation also appears to increases as the thickness difference and the viscosity difference between the two glass sheets increases.
  • Applicant has identified various separation materials, separation layer structures and/or separation material application processes that decrease or eliminate bending dot formation, even with large differences in glass sheet thickness and glass sheet viscosities. For example, Applicant has identified that lubricating materials that decrease friction between the two glass sheets decreases/eliminates bending dot formations. As a specific example, Applicant has identified that separation powders having lamellar structure and/or having a high lubricity decreases/eliminates bending dot formation. In particular, Applicant has found that a separation material comprising hexagonal boron nitrite particles and/or graphite particles decreases/eliminates bending dot formation.
  • Applicant has determined that applying the separation material through a spraying process (e.g., spraying a liquid containing the separation material, flame pyrolysis, etc.) also appears to decrease/eliminate bending dot formation.
  • a spraying process e.g., spraying a liquid containing the separation material, flame pyrolysis, etc.
  • spray application of the separation material may result in a uniform, low thickness layer of separation material that evenly distributes the contact pressure in a way that avoids bending dot formation.
  • system 10 includes one or more sheet of glass material, shown as a pair of glass sheets 12 and 14, supported by a shaping frame, shown as bending ring 16.
  • bending ring 16 may have a wide variety of shapes selected based on the shape of the glass sheets to be supported, and use of the term ring does not necessarily denote a circular shape.
  • a separation material 18 is applied to at least one surface of glass sheet 12 and/or of glass sheet 14. In one specific embodiment, separation material 18 is applied to an upper surface of lower glass sheet 12. In other embodiments, separation material 18 is applied to a lower surface of glass sheet 14. In such embodiments, separation material 18 may be applied to a surface of glass sheet 12 and/or 14 when the glass sheets are positioned in any orientation, and the terms upper and lower refer to the orientation of surfaces when supported for bending on ring 16.
  • separation material 18 is a material that prevents sheets 12 and 14 from bonding together during the heating stages of the curve formation, and as will be discussed in more detail below, separation material 18 is formed from a material and/or is applied in a manner that Applicant has identified as being effective at reducing bending dot formation.
  • bending ring 16 includes a support wall, shown as sidewall 20, and a bottom wall 22.
  • Sidewall 20 extends upward and away from bottom wall 22.
  • the radially inward facing surface 24 of sidewall 20 defines an open central region or cavity 26, and an upward facing surface of bottom wall 22 defines the lower end of cavity 26.
  • a radially outward facing surface 25 is opposite of inward facing surface 24.
  • Separation material 18 is applied to the upper surface of glass sheet 12. Upper glass sheet 14 is placed onto separation material 18 such that a lower surface of upper glass sheet 14 is in contact with separation material 18. As can be seen in FIGS. 1 and 2 , in this arrangement, separation material 18 acts as a barrier between glass layers 12 and 14 which prevents the glass sheets 12 and 14 from bonding together at the high temperatures during the sagging process.
  • an outer region 28 of glass sheet 12 adjacent the outer perimeter edge 30 of the glass sheet is placed into contact with a support surface, shown as upward facing surface 32, of bending ring 16.
  • a support surface shown as upward facing surface 32, of bending ring 16.
  • glass sheets 12 and 14 are both supported by the contact between upward facing surface 32 with glass sheet 12 such that central regions 34 of glass sheets 12 and 14 are supported over central cavity 26.
  • bending ring 16, supported glass sheets 12 and 14 and separation material 18 are moved into a heating station 40, such as an oven or serial indexing lehr.
  • a heating station 40 glass sheets 12 and 14, separation material 18 and bending ring 16 are heated (e.g., to near or at the softening temperature of the glass material of glass sheets 12 and 14) while glass sheets 12 and 14 are supported on bending ring 16.
  • a shaping force such as the downward force 42, causes central region 34 of glass sheets 12 and 14 to deform or sag downward into central cavity 26 of bending ring 16.
  • the downward force is provided by gravity.
  • the downward force 42 may be provided via air pressure (e.g., creating a vacuum on the convex side of glass sheets 12 and 14, blowing air on the concave side of glass sheets 14) or through a contact-based molding machine (e.g., co-pressing equipment).
  • cavity 26 is a mold cavity, and in such embodiments, inward facing surface 24 of sidewall 20 and the upward facing surface of bottom wall 22 defines a shape against which glass sheets 12 and 14 pressed to form a desired curved shape. Regardless of the source of the deforming force, this procedure results in glass sheets 12 and 14 having a generally curved shape, as represented in FIG. 3 .
  • bending ring 16 along with the supported glass sheets 12 and/or 14 are then cooled to room temperature.
  • the shaped, deformed or curved glass sheets 12 and 14 are allowed to cool, fixing glass sheets 12 and 14 into the curved shape created within heating station 40.
  • curved glass sheets 12 and 14 are removed from bending ring 16 and another set of flat glass sheets are placed onto bending ring 16, and the shaping process is repeated.
  • the now curved glass sheets 12 and 14 are bonded together (e.g., typically via a polymer interlayer) into the final curved glass, laminate article.
  • glass sheets 12 and 14 may be particularly susceptible to bending dot formation, at least if a conventional separation material were used, due to large thickness differences and/or material differences between glass sheets 12 and 14.
  • separation material 18 enables co-sagging of glass sheets 12 and 14 even with large thickness differentials.
  • glass sheet 12 has a thickness, shown as T1
  • glass sheet 14 has a thickness, shown as T2.
  • T1 is different from T2, and specifically T1 is greater than T2.
  • T1 is at least 2.5 times greater than T2, and in other embodiments, T2 is at least 2.5 times greater than T1.
  • T1 is between 1.5 mm and 4 mm, and T2 is between 0.3 mm and 1 mm, and in even more specific embodiments, T2 is less than 0.6 mm.
  • T1 is 1.6 mm and T2 is .55 mm; T1 is 2.1 mm and T2 is .55 mm; T1 is 2.1 mm and T2 is 0.7 mm; T1 is 2.1 mm and T2 is 0.5 mm; T1 is 2.5 mm and T2 is 0.7 mm.
  • the thicker glass sheet 12 is located below the thinner glass sheet 14 when stacked on bending ring 16.
  • some sources have indicated that placing the thicker sheet above the thinner sheet on the bending ring will decrease bending dot formation.
  • Applicant has determined that this prior approach is not particularly effective at reducing bending dot formation, particularly when large sheet thickness differentials and/or large viscosity differences are present, and the separation materials discussed herein have been determined to be effective at reducing or eliminating bending dot formation in these cases.
  • the separation material innovations discussed herein may be utilized in co-sagging arrangements where the thinner glass sheet 14 is located below thicker glass sheet 12 in the stack supported by bending ring 16.
  • the separation materials discussed herein have been determined to be particularly suitable for co-sagging glass sheets 12 and 14 formed from different glass materials. As noted above, it is believed that when glass sheets of different materials are co-sagged together, viscosity differences between the two materials at the co-sagging temperature results in increased contact pressures in the regions where sagging shape is different (e.g., see FIGS. 6 and 7 ). Applicant has determined that the separation material innovations discussed herein decrease or eliminate bending dot formation even when co-sagging glass sheets of different materials.
  • glass sheet 12 is formed from a first glass material/composition
  • glass sheet 14 is formed from a second glass material/composition different from the first material.
  • the first glass material has a viscosity that is different from the viscosity of the second glass material during heating within heating station 40.
  • the first glass material of sheet 12 is a soda lime glass
  • the second glass material of sheet 14 is an alkali aluminosilicate glass composition or an alkali aluminoborosilicate glass composition. Additional exemplary materials for glass sheets 12 and 14 are identified in detail below.
  • separation material 18 is a particulate material that is applied to the upper surface of glass sheet 12 forming a layer of particular material 50 as shown in FIG. 4 .
  • separation material 18 is formed from a solid lubricating material that decreases friction between glass sheet 12 and glass sheet 14. Without wishing to be bound by theory, Applicant's testing has indicated that decreasing friction between glass sheets 12 and 14 during co-sagging decreases bending dot formation.
  • the solid lubricating material has a lamellar structure, and specifically is an inorganic lubricating material having a lamellar structure.
  • the solid lubricating material is a hexagonal boron nitride material and/or a graphite material. These lamellar, inorganic solid lubricants are believed to have lubricity that are higher than conventional separation materials.
  • separation material 18 may be a CaCO 3 material, a silica-based material, a hydrated magnesium silicate material, and/or a molybdenum disulfide material.
  • HBN hexagonal boron nitride
  • the layered structure of HBN allows sliding movement of the parallel planes. Weak bonding between the planes provides low shear strength in the direction of the sliding movement but high compression strength in the direction perpendicular to the sliding movement.
  • HBN forms a lubrication film strongly adhered to the substrate surface. The lubrication film provides good wear resistance and seizure resistance (compatibility).
  • Boron nitride is a chemically inert substance. It is non-reactive to most acids, alkalis, solvents and non-wetted by molten aluminum, magnesium, molten salts and glass.
  • Hexagonal boron nitride retains its lubrication properties up to 5000 °F (2760 °C) in inert or reducing environment and up to 1600 °F (870 °C) in oxidizing atmosphere.
  • boron nitride has high thermal conductivity.
  • graphite and/or molybdenum disulfide may be used as solid lubricants for separation material 18.
  • these materials are effective lubricant additives due to their lamellar structure. The lamellas orient parallel to the surface in the direction of motion. Even between highly loaded stationary surfaces, the lamellar structure of these materials is able to prevent contact between glass sheets 12 and 14. In the direction of motion, the lamellas easily shear over each other resulting in a low friction.
  • separation material 18 may be other solid lubricating materials including polytetrafluorethylene (PTFE), talc, calcium fluoride, cerium fluoride and tungsten disulfide.
  • separation material 18 may be a friction or contact pressure reducing sheet of material such as a cloth sheet. In other embodiments, separation material 18 may be a thick layer of CaCO 3 material. In contrast to conventional understanding, Applicant has found that increasing thickness of a CaCO 3 separation material layer 50 actually reduces bending dot formation.
  • separation material 18 may be applied to the upper surface of glass sheet 12 via a spraying process. Applicant believes that utilizing a spraying process (as opposed to roll-based powder applicators typically used in conventional processes) results in a thin, yet highly uniform layer of separation material 18 that decreases bending dot formation.
  • separation material 18 is a solid lubricating material suspended in a carrier fluid (e.g., water, alcohol, gas, etc.), and separation material 18 is applied to the upper surface of glass sheet 12 by spraying the carrier fluid supporting the solid lubricating material onto glass sheet 12.
  • a carrier fluid e.g., water, alcohol, gas, etc.
  • the carrier fluid is a liquid
  • the carrier fluid when the carrier fluid evaporates, a thin and uniform layer of the solid lubricating particles remain on glass sheet 12 forming separation layer 50 shown in FIG. 4 .
  • the carrier fluid is a gas
  • the gas stream delivers lubricating particles to the glass surface, forming a thin and uniform layer of the solid lubricating particles on glass sheet 12 to create separation layer 50 shown in FIG. 4 .
  • a boron nitride material or a silica-based lubricating material is applied via a spraying process utilizing a carrier fluid.
  • a silica-based lubricating material comprises a Lo-Vel HSF material available from PPG Industries, Inc. dispersed in a water solution and sprayed onto glass sheet 12 forming separation layer 50.
  • separation material 18 may be sprayed onto glass sheet via other spraying processes.
  • the separation material 18 is a solid lubricating material, such as graphite, which is sprayed on to glass sheet 12 via a flame pyrolysis process.
  • glass sheet 12 or 14 are cut from their individual stock glass sheets 52.
  • the shape of the perimeter 54 is defined by a flat pattern as needed to produce the desired shape following co-sagging.
  • the edges may be ground to break the sharp corners. Following this process, glass sheets 12 and 14 are stacked and co-sagged as explained above regarding FIGS. 1-4 .
  • a curved glass laminate article formed from the process and/or system discussed herein includes sheets 12 and 14 bound together by an interlayer (e.g., a polymer interlayer such as a polyvinyl butyral layer).
  • the glass laminate article formed from glass sheets 12 and 14 is highly asymmetrical (e.g., has the large thickness differences and/or material property differences discussed above) while at the same time having low levels of bending dot defects and low levels of shape difference between the layers.
  • glass sheets 12 and/or 14 following curve formation may be utilized in a variety of applications.
  • the glass laminate article produced via the systems and processes discussed herein are used to form vehicle (e.g., automotive) windows.
  • the laminate article formed from glass sheets 12 and/or 14 may form the sidelights, windshields, rear windows, windows, rearview mirrors, and sunroofs of a vehicle.
  • vehicle includes automobiles, rolling stock, locomotive, boats, ships, and airplanes, helicopters, drones, space craft and the like.
  • the laminate article formed from glass sheets 12 and/or 14 may be used in a variety of other applications where thin, curved glass laminate articles may be advantageous, such as for architectural glass, building glass, etc.
  • Glass sheets 12 and/or 14 can be formed from a variety of materials.
  • glass sheet 14 is formed from a chemically strengthened alkali aluminosilicate glass composition or an alkali aluminoborosilicate glass composition
  • glass sheet 12 is formed from a soda lime glass (SLG) composition.
  • SSG soda lime glass
  • glass sheets 12 and/or 14 are formed from a chemically strengthened material, such as an alkali aluminosilicate glass material or an alkali aluminoborosilicate glass composition, having a chemically strengthened compression layer having a depth of compression (DOC) in a range from about 30 ⁇ m to about 90 ⁇ m, and a compressive stress on at least one of the sheet's major surfaces of between 300 MPa to 1000 MPa.
  • DOC depth of compression
  • the chemically strengthened glass is strengthened through ion exchange
  • glass sheets 12 and/or 14 may be formed from any of a variety of strengthened glass compositions.
  • glasses that may be used for glass sheets 12 and/or 14 described herein may include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, though other glass compositions are contemplated.
  • Such glass compositions may be characterized as ion exchangeable.
  • ion exchangeable means that the layer comprising the composition is capable of exchanging cations located at or near the surface of the glass layer with cations of the same valence that are either larger or smaller in size.
  • the glass composition of glass sheets 12 and/or 14 comprises SiO 2 , B 2 O 3 and Na 2 O, where (SiO 2 + B 2 O 3 ) ⁇ 66 mol. %, and Na 2 O ⁇ 9 mol. %.
  • Suitable glass compositions for glass sheets 12 and/or 14, in some embodiments, further comprise at least one of K 2 O, MgO, and CaO.
  • the glass compositions used in glass sheets 12 and/or 14 can comprise 61-75 mol.% SiO 2 ; 7-15 mol.% Al 2 O 3 ; 0-12 mol.% B 2 O 3 ; 9-21 mol.% Na 2 O; 0-4 mol.% K 2 O; 0-7 mol.% MgO; and 0-3 mol.% CaO.
  • a further example of glass composition suitable for glass sheets 12 and/or 14 comprises: 60-70 mol.% SiO 2 ; 6-14 mol.% Al 2 O 3 ; 0-15 mol.% B 2 O 3 ; 0-15 mol.% Li 2 O; 0-20 mol.% Na 2 O; 0-10 mol.% K 2 O; 0-8 mol.% MgO; 0-10 mol.% CaO; 0-5 mol.% ZrO 2 ; 0-1 mol.% SnO 2 ; 0-1 mol.% CeO 2 ; less than 50 ppm As 2 O 3 ; and less than 50 ppm Sb 2 O 3 ; where 12 mol.% ⁇ (Li 2 O + Na 2 O + K 2 O) ⁇ 20 mol.% and 0 mol.% ⁇ (MgO + CaO) ⁇ 10 mol.%.
  • glass composition suitable for glass sheets 12 and/or 14 comprises: 63.5-66.5 mol.% SiO 2 ; 8-12 mol.% Al 2 O 3 ; 0-3 mol.% B 2 O 3 ; 0-5 mol.% Li 2 O; 8-18 mol.% Na 2 O; 0-5 mol.% K 2 O; 1-7 mol.% MgO; 0-2.5 mol.% CaO; 0-3 mol.% ZrO 2 ; 0.05-0.25 mol.% SnO 2 ; 0.05-0.5 mol.% CeO 2 ; less than 50 ppm As 2 O 3 ; and less than 50 ppm Sb 2 O 3 ; where 14 mol.% ⁇ (Li 2 O + Na 2 O + K 2 O) ⁇ 18 mol.% and 2 mol.% ⁇ (MgO + CaO) ⁇ 7 mol.%.
  • an alkali aluminosilicate glass composition suitable for glass sheets 12 and/or 14 comprises alumina, at least one alkali metal and, in some embodiments, greater than 50 mol.% SiO 2 , in other embodiments at least 58 mol.% SiO 2 , and in still other embodiments at least 60 mol.% SiO 2 , wherein the ratio ((Al 2 O 3 + B 2 O 3 )/ ⁇ modifiers)>1, where in the ratio the components are expressed in mol.% and the modifiers are alkali metal oxides.
  • This glass composition in particular embodiments, comprises: 58-72 mol.% SiO 2 ; 9-17 mol.% Al 2 O 3 ; 2-12 mol.% B 2 O 3 ; 8-16 mol.% Na 2 O; and 0-4 mol.% K 2 O, wherein the ratio((Al 2 O 3 + B 2 O 3 )/ ⁇ modifiers)>1.
  • glass sheets 12 and/or 14 may include an alkali aluminosilicate glass composition comprising: 64-68 mol.% SiO 2 ; 12-16 mol.%Na 2 O; 8-12 mol.% Al 2 O 3 ; 0-3 mol.% B 2 O 3 ; 2-5 mol.% K 2 O; 4-6 mol.% MgO; and 0-5 mol.% CaO, wherein: 66 mol.% ⁇ SiO 2 + B 2 O 3 + CaO ⁇ 69 mol.%; Na 2 O + K 2 O + B 2 O 3 + MgO + CaO + SrO > 10 mol.%; 5 mol.% ⁇ MgO + CaO + SrO ⁇ 8 mol.%; (Na 2 O + B 2 O 3 ) - Al 2 O 3 ⁇ 2 mol.%; 2 mol.% ⁇ Na 2 O - Al 2 O 3 ⁇ 6 mol.%; and 4 mol.% ⁇ (Na 2 O +
  • glass sheets 12 and/or 14 may comprise an alkali aluminosilicate glass composition comprising: 2 mol% or more of Al 2 O 3 and/or ZrO 2 , or 4 mol% or more of Al 2 O 3 and/or ZrO 2 .
  • glass sheets 12 and/or 14 comprise a glass composition comprising SiO 2 in an amount in the range from about 67 mol% to about 80 mol%, Al 2 O 3 in an amount in a range from about 5 mol% to about 11 mol%, an amount of alkali metal oxides (R 2 O) in an amount greater than about 5 mol% (e.g., in a range from about 5 mol% to about 27 mol%).
  • the amount of R 2 O comprises Li 2 O in an amount in a range from about 0.25 mol% to about 4 mol%, and K 2 O in an amount equal to or less than 3 mol%.
  • the glass composition includes a non-zero amount of MgO, and a non-zero amount of ZnO.
  • glass sheets 12 and/or 14 are formed from a composition that exhibits SiO 2 in an amount in the range from about 67 mol% to about 80 mol%, Al 2 O 3 in an amount in the range from about 5 mol% to about 11 mol%, an amount of alkali metal oxides (R 2 O) in an amount greater than about 5 mol% (e.g., in a range from about 5 mol% to about 27 mol%), wherein the glass composition is substantially free of Li 2 O, and a non-zero amount of MgO; and a non-zero amount of ZnO.
  • SiO 2 in an amount in the range from about 67 mol% to about 80 mol%
  • Al 2 O 3 in an amount in the range from about 5 mol% to about 11 mol%
  • R 2 O alkali metal oxides
  • glass sheets 12 and/or 14 are an aluminosilicate glass article comprising: a glass composition comprising SiO 2 in an amount of about 67 mol% or greater; and a sag temperature in a range from about 600 °C to about 710 °C.
  • glass sheets 12 and/or 14 are formed from an aluminosilicate glass article comprising: a glass composition comprising SiO 2 in an amount of about 68 mol% or greater; and a sag temperature in a range from about 600 °C to about 710 °C (as defined herein).
  • glass sheets 12 and/or 14 are formed from different glass materials from each other that differs in any one or more of composition, thickness, strengthening level, and forming method (e.g., float formed as opposed to fusion formed).
  • glass sheets 12 and/or 14 described herein have a sag temperature of about 710 °C, or less or about 700 °C or less.
  • one of the glass sheets 12 and 14 is a soda lime glass sheet, and the other of the glass sheets 12 and 14 is any one of the non-soda lime glass materials discussed herein.
  • glass sheets 12 and/or 14 comprises a glass composition comprising SiO 2 in an amount in the range from about 68 mol% to about 80 mol%, Al 2 O 3 in an amount in a range from about 7 mol% to about 15 mol%, B 2 O 3 in an amount in a range from about 0.9 mol% to about 15 mol%; a non-zero amount of P 2 O 5 up to and including about 7.5 mol%, Li 2 O in an amount in a range from about 0.5 mol% to about 12 mol%, and Na 2 O in an amount in a range from about 6 mol% to about 15 mol%.
  • the glass composition of glass sheets 12 and/or 14 may include an oxide that imparts a color or tint to the glass articles.
  • the glass composition of glass sheets 12 and/or 14 includes an oxide that prevents discoloration of the glass article when the glass article is exposed to ultraviolet radiation. Examples of such oxides include, without limitation, oxides of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ce, W, and Mo.
  • Glass sheets 12 and/or 14 may have a refractive index in the range from about 1.45 to about 1.55. As used herein, the refractive index values are with respect to a wavelength of 550 nm. Glass sheets 12 and/or 14 may be characterized by the manner in which it is formed. For instance, glass sheets 12 and/or 14 maybe characterized as float-formable (i.e., formed by a float process), down-drawable and, in particular, fusion-formable or slot-drawable (i.e., formed by a down draw process such as a fusion draw process or a slot draw process). In one or more embodiments, glass sheets 12 and/or 14 described herein may exhibit an amorphous microstructure and may be substantially free of crystals or crystallites. In other words, in such embodiments, the glass articles exclude glass-ceramic materials.
  • glass sheets 12 and/or 14 exhibits an average total solar transmittance of about 88% or less, over a wavelength range from about 300 nm to about 2500 nm, when glass sheets 12 and/or 14 has a thickness of 0.7 mm.
  • glass sheets 12 and/or 14 exhibits an average total solar transmittance in a range from about 60% to about 88%, from about 62% to about 88%, from about 64% to about 88%, from about 65% to about 88%, from about 66% to about 88%, from about 68% to about 88%, from about 70% to about 88%, from about 72% to about 88%, from about 60% to about 86%, from about 60% to about 85%, from about 60% to about 84%, from about 60% to about 82%, from about 60% to about 80%, from about 60% to about 78%, from about 60% to about 76%, from about 60% to about 75%, from about 60% to about 74%, or from about 60% to about 72%.
  • glass sheets 12 and/or 14 exhibit an average transmittance in the range from about 75% to about 85%, at a thickness of 0.7 mm or 1 mm, over a wavelength range from about 380 nm to about 780 nm.
  • the average transmittance at this thickness and over this wavelength range may be in a range from about 75% to about 84%, from about 75% to about 83%, from about 75% to about 82%, from about 75% to about 81%, from about 75% to about 80%, from about 76% to about 85%, from about 77% to about 85%, from about 78% to about 85%, from about 79% to about 85%, or from about 80% to about 85%.
  • glass sheets 12 and/or 14 exhibits T uv-380 or T uv-400 of 50% or less (e.g., 49% or less, 48% or less, 45% or less, 40% or less, 30% or less, 25% or less, 23% or less, 20% or less, or 15% or less), at a thickness of 0.7 mm or 1 mm, over a wavelength range from about 300 nm to about 400 nm.
  • glass sheets 12 and/or 14 may be strengthened to include compressive stress that extends from a surface to a depth of compression (DOC).
  • DOC depth of compression
  • the compressive stress regions are balanced by a central portion exhibiting a tensile stress.
  • the stress crosses from a positive (compressive) stress to a negative (tensile) stress.
  • glass sheets 12 and/or 14 may be strengthened mechanically by utilizing a mismatch of the coefficient of thermal expansion between portions of the article to create a compressive stress region and a central region exhibiting a tensile stress.
  • the glass article may be strengthened thermally by heating the glass to a temperature below the glass transition point and then rapidly quenching.
  • glass sheets 12 and/or 14 may be chemically strengthening by ion exchange.
  • ions at or near the surface of glass sheets 12 and/or 14 are replaced by - or exchanged with - larger ions having the same valence or oxidation state.
  • ions in the surface layer of the article and the larger ions are monovalent alkali metal cations, such as Li + , Na + , K + , Rb - , and Cs + .
  • monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag + or the like.
  • the monovalent ions (or cations) exchanged into glass sheets 12 and/or 14 generate a stress.
  • Applicant has conducted a number of experiments to understand and evaluate bending dot formation during co-sagging of high asymmetry glass pairs as discussed herein.
  • PPG Lo-Vel HSF (a commercially available, silica based, powder) was used as a separation powder.
  • standard powder application techniques e.g., lightly brushed onto the surface, roll application (i.e. like a paint roller) or gravity (a roller is rolled over a screen which causes the powder to fall onto the surface below resulting in a light dusting)
  • Lo-Vel HSF was not effective at eliminating bending dots for gravity co-sagging of asymmetric glass sheets.
  • Lo-Vel HSF was dispersed in a water solution and applied via spray application, significant improvement in the reduction of bending dots for asymmetric glass plies was demonstrated. This indicates utilizing of spray application of the separation material can reduce bending dot formation.
  • Applicant conducted tests utilizing flame deposited carbon and spray application of hexagonal boron nitride as the separation material, and these tests demonstrated that both were highly effective at minimizing and eliminating bending dot formation. Based on these tests, Applicant believes that the uniform application of these inorganic lubricants via the spray application process combined with their highly lubricous, lamellar structure reduces the contact pressure between the asymmetric glass plies during co-sagging and minimizes or eliminates the formation of bending dots.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)

Claims (15)

  1. Verfahren zum Ausbilden eines gekrümmten Glaslaminatartikels, umfassend:
    Auftragen eines Trennmaterials auf mindestens eine Oberfläche einer ersten Glasmaterialplatte oder eine Oberfläche einer zweiten Glasmaterialplatte;
    Setzen eines Außenbereichs der ersten Glasmaterialplatte in Kontakt mit einer Auflagefläche eines Formgebungsrahmen, wobei der Formgebungsrahmen einen offenen zentralen Hohlraum definiert, der zumindest zum Teil von der Auflagefläche umgeben ist;
    Setzen der zweiten Glasmaterialplatte auf die erste Glasmaterialplatte derart, dass das Trennmaterial sich zwischen einer Oberseite der ersten Glasmaterialplatte und einer Unterseite der zweiten Glasmaterialplatte befindet, wobei die erste Glasmaterialplatte und die zweite Glasmaterialplatte beide durch den Formgebungsrahmen getragen sind; und
    Erwärmen der ersten Glasmaterialplatte, des Trennmaterials und der zweiten Glasmaterialplatte miteinander, während sie vom Formgebungsrahmen getragen sind, derart, dass sich zentrale Bereiche der ersten und zweiten Glasmaterialplatte nach unten in den offenen Hohlraum des Formgebungsrahmens hinein verformen;
    wobei die erste Glasmaterialplatte eine mittlere Dicke, T1, hat, und die zweiten Glasmaterialplatte eine mittlere Dicke, T2, hat, wobei T1 mindestens 2,5 mal T2 beträgt; und
    das Trennmaterial eine festes Schmiermaterial umfasst, das eine Reibung zwischen den ersten und zweiten Glasmaterialplatten senkt, wobei das feste Schmiermaterial eine lamellare Struktur umfasst.
  2. Verfahren nach Anspruch 1, wobei T1 zwischen 1,5 mm und 4 mm beträgt, und T2 zwischen 0,3 mm und 1 mm beträgt.
  3. Verfahren nach Anspruch 1, wobei T2 weniger als 0,6 mm beträgt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei die erste Glasmaterialplatte aus einer ersten Glaszusammensetzung gebildet ist, und die zweite Glasmaterialplatte aus einer zweiten Glaszusammensetzung gebildet ist, die sich von der ersten Glaszusammensetzung unterscheidet, und die erste Glaszusammensetzung eine Viskosität während der Erwärmung hat, die sich von einer Viskosität der zweiten Glaszusammensetzung während der Erwärmung unterscheidet.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das Trennmaterial über einen Sprühvorgang aufgetragen wird.
  6. Verfahren nach Anspruch 5, wobei der Sprühvorgang umfasst, ein von einem Trägerfluidum gehaltenes Partikelmaterial auf die erste Glasmaterialplatte zu sprühen, und/oder einen Flammenpyrolysevorgang umfasst.
  7. Verfahren nach Anspruch 6, wobei das Trägerfluidum Wasser, Alkohol oder ein Gas umfasst.
  8. Verfahren nach Anspruch 7, wobei das Trägerfluidum verdampft, indem es eine Schicht des Partikelmaterials auf der ersten Glasmaterialplatte bildet.
  9. Verfahren nach Anspruch 1, wobei das Auftragen umfasst:
    Sprühen des Trennmaterials auf die Oberfläche der ersten Glasmaterialplatte und/oder die Oberfläche der zweiten Glasmaterialplatte; und
    wobei die erste Glasmaterialplatte aus einer ersten Glaszusammensetzung gebildet ist, und die zweite Glasmaterialplatte aus einer zweiten Glaszusammensetzung gebildet ist, die sich von der ersten Glaszusammensetzung unterscheidet.
  10. Verfahren nach Anspruch 9, wobei das Trennmaterial ein Bornitridmaterial, ein Grafitmaterial, ein CaCO3-Material, ein Material auf Siliciumoxidbasis, ein hydrathaltiges Magnesiumsilikatmaterial oder ein Molybdän-Disulfid-Material umfasst.
  11. Verfahren nach Anspruch 9, wobei es sich bei der ersten Glaszusammensetzung um Kalknatronglas handelt, und es sich bei der zweiten Glaszusammensetzung um eine Alkali-Aluminoosilikatglaszusammensetzung oder eine Alkali-Aluminoborsilikatglaszusammensetzung handelt.
  12. Verfahren nach Anspruch 1, wobei das feste Schmiermaterial hexagonales Bornitrid und/oder Grafit ist.
  13. Gekrümmter Glaslaminatartikel, der durch das Verfahren nach einem der Ansprüche 1 bis 12 hergestellt ist.
  14. Gekrümmter Glaslaminatartikel nach Anspruch 13, wobei der gekrümmte Glaslaminatartikel ein Fahrzeugfenster ist.
  15. Gekrümmter Glaslaminatartikel nach Anspruch 14, wobei es sich bei dem Fahrzeugfenster um eine Seitenscheibe, eine Windschutzscheibe, eine Heckscheibe, einen Rückspiegel oder ein Schiebedach handelt.
EP18730509.9A 2017-05-17 2018-05-15 Verfahren zur herstellung gekrümmter glaslaminatartikel mit trennmaterial und produkt Active EP3625182B1 (de)

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US20200140317A1 (en) 2020-05-07
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